WO1994014820A1 - Silylurees cycliques et procede de preparation - Google Patents

Silylurees cycliques et procede de preparation Download PDF

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Publication number
WO1994014820A1
WO1994014820A1 PCT/US1993/012473 US9312473W WO9414820A1 WO 1994014820 A1 WO1994014820 A1 WO 1994014820A1 US 9312473 W US9312473 W US 9312473W WO 9414820 A1 WO9414820 A1 WO 9414820A1
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group
carbon atoms
formula
methyl
hydrogen
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Inventor
Enrico James Pepe
Curtis Louis Schilling, Jr.
Everett Wyman Bennett
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OSI Specialties Inc
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OSI Specialties Inc
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Application filed by OSI Specialties Inc filed Critical OSI Specialties Inc
Priority to EP94905481A priority Critical patent/EP0631582B1/fr
Priority to JP51540794A priority patent/JP3329388B2/ja
Priority to DE69329967T priority patent/DE69329967T2/de
Publication of WO1994014820A1 publication Critical patent/WO1994014820A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1888—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of other Si-linkages, e.g. Si-N
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888

Definitions

  • the present invention relates to cyclic silylureas and their preparation, to their
  • the present invention relates to cyclic silylureas which retain the cyclosilazane ring structure after formation. Cyclic silylureas of the present invention are used as additives in
  • RTV room temperature vulcanizing
  • VOC volatile organic compound
  • Fast curing can be attained with systems based on a polyfunctional silazane (i.e., compounds with Si-N bonds) as curing agents.
  • a polyfunctional silazane i.e., compounds with Si-N bonds
  • Such systems typically cure by releasing low molecular weight organic amines or ammoni a , which are envi ronmenta l ly undesi rable because of unacceptable odor and toxicity.
  • Cyclosilazanes and derivatives are compounds with Si-N bonds which cure at high rates by cleaving the Si-N bond without release of volatile organic compounds.
  • Cyclosilazanes have not achieved commercial acceptance in the industry because of the inability to produce them easily and in large quantity.
  • cyclosilazane-based curing agents for silicone and related adhesive systems which can be prepared in commercial equipment with high efficiency at
  • cyclosilazane with an isocyanate containing moiety.
  • the cyclosilazane ring structure is retained .
  • the resultant cyclic si lylurea is stable on storage, but is highly reactive to moisture, especially when exposed to ambient moisture in air.
  • Another embodiment of the present invention provides a class of cyclosilazanes and a process for making them.
  • the cyclosilazanes of the present invention have an Si-N bond, four carbon atoms in the ring, hydrogen as the exocyclic substituent on the nitrogen atom, and exocyclic substituents on the silicon which do not interfere sterically during cyclic silylurea formation.
  • the cyclosilazanes of the present invention have an Si-N bond, four carbon atoms in the ring, hydrogen as the exocyclic substituent on the nitrogen atom, and exocyclic substituents on the silicon which do not interfere sterically during cyclic silylurea formation.
  • cyclosilazane can have exocyclic alkyl groups on a ring carbon atom.
  • cyclosilazanes of the present invention is rapid, easy to perform, and produces the desired
  • aminoalkylalkoxysilanes and their preparation. These aminoalkylalkoxysilanes are used to make cyclosilazanes.
  • the process for making the aminoalkylalkoxysilane produces a silicon compound having a sterically hindered nitrile group, which process is easy, rapid, and results a high yield of product.
  • Still another embodiment of the present invention provides a sealant formulation containing the cyclic silylurea which cures or sets up rapidly.
  • Cyclic silylureas of the present invention are prepared by a process which comprises contacting a cyclosilazane with an isocyanate group containing moiety according to Process A as follows: cycl osi l azane i socyanate cycl i c si l yl urea
  • R is an alkyl group having 1 to 3 carbon atoms, and preferably each R is a methyl group or an ethyl group.
  • each R 1 in Formulae I and III is a hydrogen or a methyl group.
  • a is 0, 1 or 2. It is to be understood that the R groups shown in Formulae I and III can be the same as or different from one another; likewise, the R 1 groups can be the same as or different from one another.
  • c is a number ranging from 1 to 5 inclusive, preferably 1 to 3, and d is a number less than or equal to c. It is
  • R 2 can be a mono-, di- or polyvalent organic or
  • R 2 is selected from the group consisting of (i) through (vi) below.
  • Suitable alkyl groups can be
  • Suitable aryl groups can include, for example, phenyl and naphthyl.
  • alkaryl or aralkyl group having 7 to 20 carbon atoms, preferably 7 to 11 carbon atoms, and most preferably 7 carbon atoms.
  • Suitable alkaryl and aralkyl groups can include, for example, benzyl, tolyl, xylylpropyl, phenylethyl, and 3-isopropenyl- dimethylbenzyl.
  • alkarylene group having 7 to 28 carbon atoms, preferably 7 to 17 carbon atoms, and most preferably 7 or 13 carbon atoms.
  • Suitable alkarylene groups can include, for example, 2,4-tolylene as in toluene diisocyanate (TDI), xylylene,
  • alkyl-substituted arylene groups (v) An alkylene group having 2 to 18 carbon atoms, preferably 6 to 13 carbon atoms, and most preferably 6, 10, or 13 carbon atoms.
  • Suitable alkylene groups can include, for example,
  • hexamethylene as in hexamethylene diisocyanate
  • isophoronylene as in isophorone diisocyanate
  • bis(cyclohexylene)methane and other such divalent alkylene groups.
  • polymeric moiety can include oligomeric compounds. These moieties are typically employed in RTV
  • Such moieties can include, for example, a polyester, a polyether, a polydiene, a polyurethane, a poly(meth)acrylate, and a polyorganosilicone.
  • Such moieties when combined with the isocyanate functionality, are commercially available as polymeric isocyanates and are well known in the art, including DesmodurTM N, a partial
  • R 2 groups which are hydrocarbon groups, it is understood that such groups can include non-hydrocarbon
  • Process A of the present invention the reaction between the cyclosilazane and the isocyanate containing moiety takes place such that the product is a silylurea in which one of the urea nitrogen atoms is bonded to a silicon atom with both the nitrogen atom and the silicon atom being contained in the cyclosilazane ring.
  • reaction conditions are not narrowly critical due to the ease of reaction.
  • Process A occurs at a temperature ranging from about -10oC to 100°C, preferably 0°C to 70°C, and most preferably 0°C to 50°C.
  • Process A is conducted under a dry atmosphere of an inert gas such as nitrogen or argon, preferably nitrogen, under ambient pressure. While
  • superatmospheric and subatmospheric pressures can be employed, generally, such pressures are not required or desired.
  • an inert solvent can be employed to reduce viscosity of one or more of the reactants and/or to moderate the heat generated in Process A.
  • solvent can include aliphatic and aromatic hydrocarbons such as hexane, heptane, octane, toluene, xylene, and the like, and mixtures thereof. Petroleum ethers having a variety of boiling point ranges can be employed. Polar solvents such as tetrahydrofuran, acetonitrile, dimethyl formamide, and dimethylsulfoxide, can also be
  • a catalyst can be used in
  • Process A can be performed using a wide variety of equipment that has provision for heating and cooling, maintenance of an inert atmosphere, agitation, and ancillary devices, if desired, for filtration, stripping of solvents, and transfer of products.
  • Any cyclosilazane having the above Formula I can be used to make the cyclic silylurea of the present invention.
  • Illustrative cyclosilazanes which can be employed in the process for preparing a cyclic silylurea of the present invention include:
  • Form III can be prepared in accordance with Process B of the present invention as follows: Aminoalkylalkoxysilane cyclosilazane
  • R, R 1 and a are as defined hereinabove with respect to Formulae I and III.
  • each R 1 is a methyl or one R 1 is a methyl group and the other R 1 is a hydrogen.
  • at least one R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms.
  • the preferred aminoalkylalkoxysilanes that can be employed in Process B of the present invention include the following: H 2 NCH 2 CMe 2 CH 2 CH 2 SiMe(OMe) 2 * H 2 NCH 2 CMe 2 CH 2 CH 2 Si (OMe) 3
  • Pr is propyl It has been found that when the R 1 group is a methyl group, the cyclization reaction is
  • aminoalkylalkoxysilanes can be prepared by methods well known to those skilled in the art. Such methods include, for example, the hydrogen reduction of the corresponding nitrile-substituted alkylalkoxysilanes as disclosed in U.S. Patent Nos. 2.930,809. Process B of the present invention is so facile that it is not necessary to isolate the aminoalkylalkoxysilanes after such reduction.
  • the novel cyclosilazanes of Process B of the present invention are distilled directly from the reduction reaction mixture after simple addition of the base catalyst.
  • nitrile-substituted alkylalkoxysilanes or precursors are also well known in the art and are readily commercially available, except for the nitrile-substituted alkylalkoxysilanes which contain the -CH 2 CH 2 CMe 2 CN substituent. These latter nitrile-substituted alkylalkoxysilanes are obtained in accordance with Process C of the present invention described hereinbelow.
  • Process B is conducted in the presence of a basic catalyst.
  • the basic catalyst used in Process B is a non-volatile base of sufficient strength to catalyze the reaction, but not such that it reacts with other substituents of the aminoalkylalkoxysilane (Formula IV). It is desirable that the basic catalyst be soluble in the reaction mixture and that it not promote undesired side reactions. Therefore, preferred basic catalyst are alkali metal salts of alcohols corresponding to the alkoxy group on the aminoalkylalkoxysilane (Formula IV). For example, methoxide salts are used with
  • aminoalkylmethoxysilanes and ethoxide salts are employed with aminoalkylethyoxysilanes.
  • Any alkali metal (sodium, potassium, lithium, and cesium) alkoxide can be employed as a basic catalyst in
  • the amount of basic catalyst employed in Process B is not narrowly critical and can range from about 0.01 to 10 weight percent, preferably from about 0.05 to 2 weight percent based on the amount of aminoalkylalkoxysilane employed.
  • Process B is conducted at a temperature less than 100°C.
  • the temperature ranges from about 40°C to 90°C, most preferably it ranges from about 60°C to 85°C.
  • Process B of the present invention is carried out under a vacuum pressure ranging from about 0.1 to 20 millimeters of mercury, preferably 0.5 to 10 millimeters of mercury, and most preferably 1 to 7 millimeters of mercury.
  • Process B of the present invention lower levels of catalyst and milder reaction conditions (lower temperatures and less severe vacuum values) can be used as the number of R 1 groups which are methyl, rather than hydrogen, is increased.
  • the equipment used to perform Process B of the present invention is not narrowly critical.
  • Process B can be performed in a variety of laboratory and commercial apparatus, ranging from standard or specialized glassware to stainless steel kettles, which have provisions for charging of reactants, heating and cooling, agitation, maintenance of appropriate vacuum or inert atmosphere, and removal of products, with ancillary equipment as needed for filtration, stripping of solvents, and distillation. Generally, Process B is conducted under an atmosphere of a dry inert gas such as nitrogen or argon.
  • a dry inert gas such as nitrogen or argon.
  • Cyclic silylureas of the present invention are used as highly moisture reactive precursors to silanol functionalities. That is, in the presence of water, the Si-N bond of the cyclic silylurea readily breaks to form a linear alkylurea. The silicon atom of the linear alkylurea readily accepts an OH-group, thereby becoming more easily susceptible to further crosslinking (-Si-O-Si-). Hence, when a cyclic silylurea is employed as a component in a sealant or caulking material, the sealant dries more quickly. For example a cyclic silylurea can be used as a reactive crosslinker for a neutral cure silicone rubber.
  • a polymer or prepolymer a polymer or prepolymer, catalyst, and curing agent.
  • a solvent, plasticizer and extender are als.o used.
  • Aminoalkylalkoxysilanes that can be used in the preparation of cyclosilazanes employed in Process B of the present invention can be made according to the following Process C:
  • each R is a methyl group or an ethyl group; and each R 1 is a methyl group.
  • a nitrile (Formula V) is reacted with a vinylsilane (Formula VI) with heating in the presence of a base at or near atmospheric pressure to produce a nitrile-substituted alkylalkoxysilane (Formula VII).
  • temperatures may vary from about 50°C to 150°C, depending upon the base used to catalyze the
  • reaction temperature ranges from about 110°C to 130°C.
  • reaction is carried out with agitation at atmospheric pressure.
  • the reaction may be performed in the presence of an inert solvent such as xylene in an amount ranging from 10 to 200 percent based on the total weight of the reactants.
  • the base used to catalyze the reaction of the nitrile (Formula V) and vinylsilane (Formula VI) is selected from the group consisting of: (a) an alkali metal (sodium, potassium, cesium, and
  • an alkali metal alkoxide such as sodium or potassium methoxide
  • an alkali metal amide such as sodium amide
  • an alkali metal hydride such as sodium hydride
  • the metal is sodium. Most preferably, sodium metal is employed in order to minimize undesirable side reactions.
  • alkylalkoxysilane (Formula VII) is hydrogenated by any means known to one skilled in the art to produce the aminoalkylalkoxysilane (Formula IV), the
  • Such silanes provide properties (i.e., reactivity, basicity, resistance to oxidative color development) intermediate between 3-aminopropylalkoxysilanes and the sterically hindered
  • Patent No. 2,930,809 In general,
  • aminoalkylalkoxysilanes are prepared by reacting a nitrile-substituted alkylsilane in the presence of a Raney Ni catalyst or similar catalyst at an elevated temperature (120°C to 200°C) and super atmospheric pressure (100 to 2,000 psi).
  • distillate product was redistilled through a column (2 ft. x 1 in. diameter) packed with helix-shaped, 1/8 inch glass equipped for vacuum fractional
  • Example 2 4-Amino-3,3-dimethylbutyltrimethoxysilane (208.3 grams, 1.014 moles) was charged to a flask equipped as in Example 1. Sodium methoxide (2 grams, 1.0 weight %) was added as described in Example 2. According to analysis using gas chromatography, the cfude distillate product (176.9 grams) had 49% cyclic silazane. The crude product was redistilled as in Example 2. The yield was 90 grams (0.47 moles) of 1,1-dimethoxysila-2-aza-4,4-dimethylcyclohexane,
  • the nitrogen assay was calculated to be 5.28 meq/gram [5.30 meq/gram actual].
  • the heating mantle was removed, and the temperature of the contents in the flask was maintained at 105 to 115°C by the rate of addition of the methylvinyldimethoxysilane.
  • the contents of the flask were heated to 150°C for one hour, and then cooled to room temperature.
  • Example 2 The procedure of Example 1 was repeated, except that 3-aminopropyltrimethoxysilane (113.5 grams; 0.63 moles) was used. Sodium methoxide (2.3 grams, 2 wt.%) was added. The reaction mixture was stirred and heated to 90°C to 98°C for 6 hours at 4-8 mm Hg, while slowly removing distillate. However gas chromatographic analysis indicated
  • 1,1-dimethoxysila-2-azacyclopentane was not formed.
  • the distillate consisted of >99% 3-aminopropyl- trimethoxysilane.
  • the reaction mixture was further heated to 130°C (>10 mm Hg) but distillate analysis again indicated no five-membered ring cyclosilazane product was formed.
  • thermometer and dropping funnel The flask was immersed in an ice bath and the mixture was cooled to about 3°C under an atmosphere of dry nitrogen gas. n-Butyl isocyanate (10.9 grams, 0.11 moles) was added dropwise for five minutes from a dropping funnel.
  • reaction mixture was heated under vacuum to 40°C at 1 mm Hg pressure to remove hexane and excess n-butyl isocyanate.
  • a white solid residue product (26.5 grams) melting at 65°C having the structure: was produced.
  • Tetraethylene glycol (349.6 grams, 1.8 moles) and 613 grams of 2-butanone were charged to a two-liter, three-necked flask equipped with
  • stannous octoate 0.175 grams, 0.02% by weight was added. The mixture was heated to gentle reflux at approximately 80°C and
  • concentration of isocyanate was 0.38 moles/kilogram, which corresponded to a molecular weight of
  • polyurethane prepolymer 300 grams, 0.069 moles NCO solution was charged to a 500 milliliter,
  • 4-amino-3-methylbutylmethyldimethoxysilane (13.2 grams, 0.069 moles) was added to the flask with stirring at 50°C for five minutes. After stirring for an additional 30 minutes at 70°C, a polyurethane prepolymer having linear silane endcapping was diluted with dry 2-butanone to 50 wt% solids and stored in a sealed bottle.
  • Control A was applied to each of the following panels: polyethylene, MylarTM, TeflonTM, steel, aluminum, glass plate, and painted glass.
  • Control A Two more sets of panels treated with beads of Control A and the novel cyclosilazane
  • end-capped polyurethane prepolymer were prepared as above and placed in an oven at 70°C for 3 hours. It was observed that the beads on the panels treated with the cyclosilazane end-capped polyurethane
  • prepolymer were firmer than those of Control A.
  • PPG-D-4000 from Olin Chemicals Inc.
  • the molar ratio of 4,4'-diphenylmethane diisocyanate to polypropylene glycol was 1.5.
  • the contents of the flask were heated to 50°C until the reaction mixture became liquid, then one drop of dibutyltin dilaurate
  • isocyanate groups decreased to about 0.8%. After cooling to room temperature, the contents of the flask (an isocyanate functional polyether prepolymer) were used as described below.
  • Control B To 80 grams of the prepolymer was slowly added 3.46 grams (10 mole % excess, based on NCO content) of 4-amino-3-methylbutyltrimethoxy- silane at room temperature in equipment as set forth in Example 11. After the addition was complete, the composition was heated with stirring to 90°C until the isocyanate concentration was 0% by titration.
  • Control C In a manner similar to that of Control B, a second 80 gram portion of the prepolymer was reacted with 3.00 grams (10 mole % excess, based on NCO content) of 3-aminopropyltrimethoxysilane. Novel Cyclosilazane (Run No. 1). In a manner similar to the preparation of Controls B and C, a third 80 gram portion of prepolymer was reacted with 2.93 grams (10 mole % excess, based on NCO content) of 1,1-dimethoxysila-2-aza-4- methylcyclohexane.
  • Sealant Preparation Sealants were prepared from each of these three silylurea linked polymers by using a small planetary mixer equipped with a vacuum pump, a temperature bath, and nitrogen and air lines. The mixer was heated to 80°C with nitrogen purging through the system for 30 minutes. Each silylurea linked polymer (80 gm.) was placed in the heated mixer, along with 24 grams of calcium
  • composition was mixed for 5 minutes in a nitrogen atmosphere followed by vacuum treatment for an additional 50 minutes.
  • Each sealant was removed from the mixer and stored in an aluminum foil/cardboard cartridge.
  • prepolymers of the present invention cure much more rapidly than those prepared from polyurethane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Sealing Material Composition (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne une classe de silylurées cycliques et un procédé pour les préparer, lequel procédé consiste à faire réagir un cyclosilazane avec une fraction contenant un isocyanate; une classe de cyclosilazanes et un procédé pour les fabriquer, lequel procédé consiste à chauffer un aminoalkylalcoxysilane en présence d'un catalyseur basique à une température inférieure à 100 °C à la pression subatmosphérique; et des aminoalkylalcoxysilanes ainsi qu'un procédé pour les fabriquer, lequel procédé consiste à faire réagir un nitrile et un vinylsilane tout en les chauffant en présence d'une base choisie dans le groupe composé de (a) un métal alcalin, (b) un alcoxyde de métal alcalin, (c) un amide de métal alcalin, (d) un hydrure de métal alcalin et (e) des mélanges de ceux-ci afin de former un produit de réaction qui est ensuite hydrogéné.
PCT/US1993/012473 1992-12-18 1993-12-20 Silylurees cycliques et procede de preparation Ceased WO1994014820A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94905481A EP0631582B1 (fr) 1992-12-18 1993-12-20 Silylurees cycliques et procede de preparation
JP51540794A JP3329388B2 (ja) 1992-12-18 1993-12-20 アミノアルキルアルコキシシラン及び製造法
DE69329967T DE69329967T2 (de) 1992-12-18 1993-12-20 Zyklische silylharnstoffe und verfahren zu deren herstellung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/993,304 1992-12-18
US07/993,304 US5354880A (en) 1992-12-18 1992-12-18 Cyclic silylureas and process of preparation

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Publication Number Publication Date
WO1994014820A1 true WO1994014820A1 (fr) 1994-07-07

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US (1) US5354880A (fr)
EP (1) EP0631582B1 (fr)
JP (2) JP3329388B2 (fr)
CA (1) CA2129958C (fr)
DE (1) DE69329967T2 (fr)
ES (1) ES2154292T3 (fr)
WO (1) WO1994014820A1 (fr)

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WO1998029418A1 (fr) * 1996-12-27 1998-07-09 Wacker-Chemie Gmbh Composes organosiliciques comportant des groupes uree, leur procede de preparation et leur utilisation
US5900315A (en) * 1997-03-06 1999-05-04 Cabot Corporation Charge-modified metal oxide particles
WO2006018143A1 (fr) * 2004-08-19 2006-02-23 Wacker Chemie Ag Composes organosilicies cycliques et leur utilisation
WO2016094186A1 (fr) * 2014-12-10 2016-06-16 Gelest Technologies, Inc. Siloxane/silsesquioxane-uréthane hybride durcissant à l'humidité rapidement et systèmes siloxane/silsesquioxane-époxy présentant des propriétés adhésives

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US5856544A (en) * 1996-04-15 1999-01-05 Osi Specialties, Inc. Aminopolysiloxanes with hindered 4-amino-3,3-dimethylbutyl groups
US5939574A (en) * 1996-04-15 1999-08-17 Witco Corporation Aminosiloxanes with 4-amino-3,3-dialkylbutyl groups
US6001946A (en) * 1996-09-23 1999-12-14 Witco Corporation Curable silane-encapped compositions having improved performances
US6693670B1 (en) * 1999-07-29 2004-02-17 Vision - Sciences, Inc. Multi-photodetector unit cell
US6310170B1 (en) 1999-08-17 2001-10-30 Ck Witco Corporation Compositions of silylated polymer and aminosilane adhesion promoters
US6197912B1 (en) 1999-08-20 2001-03-06 Ck Witco Corporation Silane endcapped moisture curable compositions
WO2003091186A2 (fr) * 2002-04-23 2003-11-06 Gelest, Inc. Azasilanes et procedes de fabrication et d'utilisation correspondants
US6673954B1 (en) * 2003-02-19 2004-01-06 General Electric Company Process for the preparation of N-silylorganocarbamates
DE102005038791A1 (de) * 2005-08-17 2007-02-22 Degussa Ag Organosiliciumverbindungen, ihre Herstellung und ihre Verwendung
US7507849B2 (en) * 2007-06-22 2009-03-24 3M Innovative Properties Company Cyclic silazanes containing an oxamido ester group and methods of making these compounds
US9040622B2 (en) 2012-05-03 2015-05-26 Ppg Industries Ohio, Inc. Solvent-based primer solution based on silylated polyurethane (SPUR) chemistry for polycarbonate substrates
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JPH07504211A (ja) 1995-05-11
CA2129958A1 (fr) 1994-07-07
EP0631582A1 (fr) 1995-01-04
JP3329388B2 (ja) 2002-09-30
US5354880A (en) 1994-10-11
JP3920650B2 (ja) 2007-05-30
EP0631582B1 (fr) 2001-02-28
DE69329967T2 (de) 2001-06-13
EP0631582A4 (fr) 1997-09-10

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